DOI: 10.1002/asia.201201089
Facile Synthesis and Photophysical Properties of Sphere–Square Shape
Amphiphiles Based on Porphyrin–[60]Fullerene Conjugates
Chien-Lung Wang,*
[a, b]Wen-Bin Zhang,
[a]Xinfei Yu,
[a]Kan Yue,
[a]Hao-Jun Sun,
[a]Chih-Hao Hsu,
[a]Chain-Shu Hsu,
[b]Jojo Joseph,
[c]David A. Modarelli,*
[c]and
Stephen Z. D. Cheng*
[a]Introduction
Driven by noncovalent interactions, self-assembling
process-es are recognized as one of the most important ways to
build up complex supramolecular entities.
[1–7]Based on
self-assembly principles, various complex functional
supramolec-ular materials have been developed.
[8–14]The synergy
be-tween geometric complementarity and noncovalent
interac-tions is the determining factor in the formation of the final
structure. Based on dimensionality and geometry,
nano-building blocks can be generally divided into four
catego-ries: spheres (0D), cylinders (1D), discs (2D), and bulk
com-plex structures (3D). Molecules consisting of geometrically
distinct
subunits
are
thus
known
as
“shape
amphi-philes”.
[15–27]Because the covalent linkage changes not only
the geometry, but also the symmetry of the molecules, the
molecular shape is also an important factor in tuning the
final self-assembled structures in addition to noncovalent
in-teractions.
Porphyrin (Por) and [60]fullerene (C
60) are representative
2D and 0D conjugated nanobuilding blocks (Scheme 1).
Al-though the major noncovalent interactions are both p–p
teractions, the shape and geometry define the favorable
in-teraction orientations and the resulting supramolecular
ar-chitectures. The 2D nanobuilding block, Por, prefers to form
columnar phases through directional face-to-face p–p
stack-ing,
[28, 29]whereas the 0D sphere, C
60
, favors the formation of
a plastic crystal phase with a face-centered cubic unit cell, in
which the p–p interaction is anisotropic.
[30]Covalently
bound Por and C
60breaks the centrosymmetry of the
origi-nal nanobuilding blocks and gives a series of intriguing Por–
C
60shape amphiphilies.
[31–38]In terms of functionality,
cova-lently bound Por and C
60forms an electron donor–acceptor
dyad. Unique photophysical properties, such as ultrafast
photoinduced charge separation, long-lived
charge-separa-tion state, ambipolar charge transport, and photovoltaic
ac-tivities, demonstrated the potential of C
60–Por shape
amphi-philes in optoelectronic applications.
[34, 36, 37, 39–43]Abstract: Molecules constructed from
a
combination
of
zero-dimensional
([60]fullerene (C
60)) and
two-dimen-sional (porphyrin (Por)) nanobuilding
blocks represent an intriguing category
of sphere–square “shape amphiphiles”.
These
sphere–square
shape
amphi-philes possess interesting
optoelectron-ic properties. To effoptoelectron-iciently synthesize
a large variety of C
60–Por shape
amphi-philes, a facile route based on Steglich
esterification was developed. The
syn-thetic strategy enables the preparation
of hydroxy-functionalized Por
precur-sors (9–12) with high purity in a
one-pot procedure. All of the C
60–Por
shape amphiphiles (1–5) can be readily
synthesized in good yields through
sub-sequent
Steglich
esterification
with
a highly soluble carboxylic acid
deriva-tive of methanofullerene (13).
Photo-physical studies indicated weak
elec-tronic coupling between the C
60and
Por moieties and suggest an
edge-to-face alignment for the moieties. The
fluorescence of electronically excited
Por portions of each amphiphile was
efficiently quenched, which was
indica-tive of electron transfer from
1Por to
the
C
60group(s).
Increasing
the
number of C
60groups on the shape
am-phiphiles led to more pronounced
quenching of the Por fluorescence,
which indicated the potential for more
effective generation of
charge-separat-ed species, C
60CPor
+C, from the
photo-excited C
60–Por shape amphiphiles.
Keywords: fullerenes ·
photophy-sics · porphyrinoids · shape
amphi-philes
[a] Prof. C.-L. Wang, W.-B. Zhang, X. Yu, K. Yue, H.-J. Sun, C.-H. Hsu, Prof. S. Z. D. Cheng
Department of Polymer Science
College of Polymer Science and Polymer Engineering The University of Akron, Akron, Ohio 44325 (USA) E-mail: [email protected]
[b] Prof. C.-L. Wang, Prof. C.-S. Hsu
Department of Applied Chemistry, National Chiao Tung University 1001 Ta Hsueh Road, Hsinchu 30010 (Taiwan)
E-mail: [email protected] [c] J. Joseph, Prof. D. A. Modarelli
Department of Chemistry and The Center for Laser and Optical Spectroscopy, Knight Chemical Laboratory The University of Akron, Akron, Ohio 44325-3601 (USA) E-mail: [email protected]
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/asia.201201089.
Recently, we reported our efforts toward self-assembled,
hierarchical “double cable” supramolecular structures in the
bulk through the design and synthesis of Por–C
60shape
am-phiphiles.
[44–46]These shape amphiphiles first form
hierarchi-cal “double cable” columns and further organize into 3D
or-thorhombic or hexagonal columnar lattices.
[45, 46]An
alternat-ing arrangement of Por and C
60in a triclinic lattice formed
by trans-diC
60–Zn
IIPor was also observed.
[44]These studies
demonstrated an abundance of supramolecular entities
formed by C
60–Por shape
am-phiphiles and their potential
use in optoelectronic
applica-tions. Because an efficient and
precise synthesis is a
prerequi-site in the study of structure–
property relationships, our
at-tention focused on extending
the previously reported
two-step esterification strategy to
the synthesis of a library of
C
60–Por shape amphiphiles for
a systematic study. The
struc-tures are thus constructed with
a single Por core, as shown in
Scheme 1. It is evident that,
not only the chemical
composi-tions (C
60/Por ratio per
mole-cule), but also the molecular
geometries, can be
systemati-cally varied. Intriguing
optoe-lectronic and self-assembly
be-havior of these molecules is
anticipated.
The
synthesis
of
Por–C
60conjugates mainly involves two
approaches: 1) condensation of
a C
60-containing component to
form the Por core;
[47–49]and
2) attaching C
60to a preformed
functionalized
Por.
[50]The
preparation of Pors through
the condensation of aldehyde
and pyrrole is known to give
a mixture of compounds that
are usually difficult to
sepa-rate.
[51, 52]The synthesis of Por–
C
60by using the first method is
thus costly. The
post-function-alization method circumvents
the difficulties associated with
Por synthesis and has become
prevalent. However, this
ap-proach is also limited by the
low solubility of both Por and
C
60and the functional group
tolerance of the coupling
reac-tion when considering the
mul-titude of functional groups in the system. Recently, click
chemistry has been applied to the synthesis of such a
con-struct with a triazole linkage.
[53–57]Our approach uses a
two-step esterification process and introduces
3,4,5-trisdodecy-loxy benzoate and 3,5-bis(dodecy3,4,5-trisdodecy-loxy)benzyl groups with
long alkyl groups to make both components highly soluble,
thereby facilitating the synthesis and purification of the final
molecule.
Herein, sequential esterification strategies were used to
effectively generate a library of C
60–Por shape amphiphiles.
First, 5,10,15,20-tetra(p-hydroxyphenyl)porphyrin (6) was
chosen as the core unit and Steglich esterification was used
to sequentially connect the peripheral substituents, which
were 3,4,5-trisdodecyloxybenzoic acid (7) and a carboxylic
acid derivative of methanofullerene (13).
[58]By taking
ad-vantage of the large polarity difference between the hydroxy
group and the ester group, all of the specifically
hydroxy-functionalized porphyrins (OH-Pors in Scheme 2) can be
prepared effectively and separated easily in a one-pot
reac-tion. The C
60–Por shape amphiphiles were then synthesized
by treating the OH-Pors with 13 through a second Steglich
esterification. This synthetic procedure has the following
ad-vantages: First, control of the number of functional groups
per Por is achieved at an early stage of the synthesis. As
shown in Scheme 3, monoOH-Por (9), 5,15-diOH-Por (10),
5,10-diOH-Por (11), and 5,10,15-triOH-Por (12) were
sepa-rated and obtained during the first step of the synthesis.
Second, the carboxylic acid derivative of methanofullerene,
which is more time-consuming and costly to prepare, is only
used in the last step of the synthesis. Third, the mild reaction
conditions of Steglich
esterifi-cation prevent potential
de-composition in the reaction to
the conjugated molecules.
Results and Discussion
Synthesis and Characterization
of the OH-Por Precursors
The synthesis of the OH-Pors
is outlined in Scheme 3. The
molecules were prepared by treating
5,10,15,20-tetra(p-hy-droxyphenyl)porphyrin with 2.2 equivalents of
3,4,5-trisde-docyloxybenzoic acid. Mixtures of the reference molecule
(8) and compounds 9, 10, 11, and 12 were obtained through
this procedure; these were readily separated by flash
column chromatography on silica gel as a result of the large
polarity differences in 8–12, thus resulting from the different
number and positions of the OH groups (polarity: 8 < 9 <
10 < 11 < 12). The yields of these reactions were 13 (8), 13
(9), 13 (10), 19 (11), and 20 % (12), with a total yield of all
products of about 78 % after purification. The molecular
structures of 8,
[29]9, 10, 11, and 12 were characterized by
1H
and
13C NMR spectroscopy and MALDI-TOF mass
spec-trometry. MALDI-TOF mass spectra clearly confirmed the
structures of 9, diOH-Por, and triOH-Por. The parent-ion
peaks observed at m/z 2648.02, 1991.39, 1991.41, and
1334.43 in Figure S1 in the Supporting Information
corre-spond to the molecular ions [M
+] of 9, 10, 11, and 12,
re-spectively, and agree well with the calculated molecular
weights of the corresponding molecules. Although the
5,15-and 5,10-isomers of the diOH-substituted compound cannot
be distinguished from their MALDI-TOF mass spectra,
their molecular symmetry is distinctly different and NMR
spectroscopy experiments can readily distinguish between
the two isomers. As shown in Figure 1, the molecular
struc-ture of 10 includes two twofold rotational axes, whereas 11
only has one. The difference in molecular symmetry leads to
different chemical environments for the b protons on the
pyrrole rings and different chemical shifts and splitting
pat-terns in the
1H NMR spectra. As a result, only one signal
was observed at d = 8.91 ppm for the b protons of 10, but
three signals were observed at d = 8.96, 8.90, and 8.82 ppm
for the b protons of 11 (Figure 1). Thus, from a combination
of molecular characterization techniques, the molecular
identities of 9–12 were established unambiguously.
Synthesis of the C
60–Por Shape Amphiphiles
As outlined in Scheme 4, the shape amphiphiles,
mono-C
60Por (1), trans-diC
60Por (2), cis-diC
60Por (3), triC
60Por (4),
and tetraC
60Por (5) were prepared by treating 9, 10, 11, 12,
and 6 separately with 13 through a second Steglich
esterifi-cation.
Scheme 2. The two-step synthetic route for preparing the C60–Por amphiphiles.
Scheme 3. Synthetic procedure for the preparation of OH-Pors 9–12. Re-agents and conditions: i) 3,4,5-trisdodecyloxybenzoic acid, N,N’-diisopro-pylcarbodiimide (DIPC), 4-(dimethylamino)pyridinium toluene-p-sulfo-nate (DPTS), tetrahydrofuran (THF)/CH2Cl21:2, 25 8C
The yields of each shape amphiphile after purification
were 71 (1), 63 (2), 83 (3), 73 (4), and 53 % (5).
Compari-sons of the
1H NMR spectra of 9 and 1 are given in
Fig-ure 2 a and b. After the esterification reaction, the protons
on the p-hydroxyphenyl group of 9 (d = 8.09 and 7.21 ppm)
shifted downfield to d = 8.26 and 7.60 ppm owing to the
res-onance effect of the electron-withdrawing carbonyl group,
and the signals of the protons on the attached C
60arm
ap-peared at d = 6.68, 6.46, 5.55, 5.37, and 3.94 ppm. In
Fig-ure S2 in the Supporting Information, the signals between
d = 136 and 146 ppm in the
13C NMR spectrum of 1
(Fig-ure S2 a) were not observed in
the
spectrum
of
9
(Fig-ure S2 b); this clearly indicates
the presence of the sp
2carbons
of the C
60unit. These results
evidently imply the formation
of an ester bond between the
OH-Por precursor and 13. The
1
H NMR spectra of 2, 3, 4, and
5 are also shown in Figure 2 c–
f. The signal of the methylene
groups next to the oxygen
atom (OCH
2) on the
3,4,5-tris(dodecyloxy)benzoate
of
the Ar
1arm appear at d =
4.15–4.19 ppm. Comparing the
integration of this signal to
those protons belonging to the
C
60units, it is clear that, as the
number of C
60units per
mole-cule increases, the integration
of this signal decreases, whereas those signals belonging to
the C
60arms show increased integration. In addition,
differ-Figure 1. Molecular structures and1H NMR spectra of a) 10 and b) 11.Scheme 4. Synthetic procedure for the preparation of C60–Por shape
am-phiphiles 1–5. Reagents and conditions: i) 13, DIPC, DPTS, CH2Cl2,
25 8C; ii) 13, DIPC, DPTS, THF/CH2Cl21:2, 25 8C.
ent molecular symmetries of 2 and 3 affect the signals of the
b protons on the pyrrole rings of the Por core. In the region
between d = 8.8 and 9.0 ppm, the b protons of the more
sym-metrical compound, 2, has two doublet signals, whereas less
symmetrical 3 has two groups of multiple signals. The
MALDI-TOF mass spectra (Figures S3–S6 in the Supporting
Information) have m/z values that closely match the
molec-ular ions [M
+] of each C
60
–Por shape amphiphile. These
combined results confirmed the success in obtaining the
C
60–Por shape amphiphiles.
Photophysical Properties of the C
60–Por Shape
Amphiphiles
The ground-state absorption spectra of the C
60–Por
amphi-philes (1–5) and reference molecules 8 and 13 were
exam-ined in THF (Figure 3). Comparison of reference
com-pounds 8 and 13 with 1–5 indicate little, if any, ground-state
electronic coupling occurs between the two chromophores.
The absorption spectra of 1–5 are similar to one another
and are characterized by absorptions in the Q-band region
at 515, 550, 590 and 646 nm, and in the more intense Soret
band region at 419 nm. The two higher energy bands at
l
max=
258 and 326 nm result from the C
60groups and the
in-tensity of these bands scales linearly with the number of C
60groups in each dyad.
Electronic coupling between the Por and C
60moieties in
covalently bound C
60–Por derivatives typically leads to
a bathochromic shift of the Soret and Q bands of the Por
moiety.
[42, 60]The degree of the bathochromic shift depends
on the relative spatial orientation of the C
60and Por
moiet-ies. Guldi et al. showed that C
60–Por dyads aligned in
face-to-face orientations underwent bathochromic shifts to
a greater extent than edge-to-face aligned C
60–Por dyads,
most likely because of stronger Por-to-C
60electronic
cou-pling present in the face-to-face aligned dyad.
[42]In the case
of 1–5, bathochromic shifts were not observed in either the
Soret or Q-band absorptions, relative to 8. Thus, electronic
coupling between Por and C
60in 1–5 is weak and the relative
position of Por and C
60in 1–5 is likely to be close to an
edge-to-face alignment. Considering the fact that the C
60moieties in 1–5 are connected to the Por core at only one
point (instead of two points in the study by Guldi et al.),
[42]the C
60groups in 1–5 are likely to be oriented away from
the Por core; this accounts for the small Por-to-C
60electron-ic coupling and lack of a bathochromelectron-ic shift in the
absorp-tion bands.
The generation of charge carriers is a critical step in the
photon-to-electron
conversion
process
in
photovoltaic
cells.
[61]Previous studies have demonstrated the potential of
C
60–Por dyads in photovoltaic applications,
[36, 37, 45, 46]in which
the generation of long-lived charge carriers makes these
ma-terials an attractive component in bulk-heterojunction
pho-tovoltaics. Great interest lies in how the variation in the C
60/
Por ratio affects the photophysical behavior of C
60–Por
shape amphiphiles. Because quenching of the Por
fluores-cence (FL) in Por-containing donor–acceptor dyads is
a good qualitative indicator of electron transfer, and
there-fore, of the generation of charge carriers,
[39–41, 43, 62]we
decid-ed to examine the FL spectra of 1–5 (Figure 4). The FL
spectrum of 8 is typical of tetraarylporphyrins, and has
emis-sion bands at l
max=
653 and 721 nm (Figure 4 a). The FL
spectra of 1–5 displayed emission bands at the same
ener-gies, but with intensities significantly reduced relative to 8.
The FL quantum yields (F
FL) of each compound were
deter-Figure 3. Normalized absorption spectra of the C60–Por shape
amphi-philes (1–5) and compounds 8 and 13 in THF.
Figure 4. a) The FL spectra of 8 and dyads 1–5 in THF. b) The quantum yields (FFL) are plotted as a function of the number of C60groups.
mined and are shown graphically in Figure 4 b. Interestingly,
the F
FLvalues decrease from 0.15 for 8 to 0.018 for 1 and
to about 0.001 for 5 as the number of C
60units increases
from one in 1 to four in 5 (Figure 4 b). The difference in F
FLbetween 2 and 3 is less pronounced. The significant decrease
in F
FLin 1–5 as a function of the number of C
60groups
pres-ent on the shape amphiphiles is consistpres-ent with previous
work,
[39–41, 43, 57]thus indicating efficient electron or energy
transfer from photoexcited Por to the C
60group; this
poten-tially leads to charge-separation (Por
+CC60
C). The specific
regiochemistry of the attachment points in multi-C
60bearing
Por shape amphiphiles appears to play a less significant role.
These preliminary results suggest the potential use of these
C
60–Pors amphiphiles as photoinduced charge-generation
materials in the active layer of photovoltaics. We are
cur-rently using transient absorption spectroscopy to determine
charge-separation and recombination rate constants in these
dyads.
Time-correlated single-photon counting (TCSPC)
experi-ments were used to measure the Por excited-state lifetimes
(t) of 1–5 and reference compound 8, and are summarized
in Table 1. Excitation was performed at the Por Q-band
ab-sorption at 560 nm in THF in these experiments, whereas
the Por emission band was monitored at 651 nm. As
expect-ed, the decay of 8 was monoexponential with a lifetime of
10.1 ns; this was consistent with the literature value of 10–
11 ns for similar Pors.
[63]The decays for dyads 1–5 were
con-siderably shorter than that of 8 and were best fit by using
two- or three-component global analysis (Table 1). The
life-time recorded for 1 is characterized by one longer-lived
component of 2.16 ns comprising 86 % of the decay and
a second, shorter lifetime of 499 ps (9 %). The data for 2
and 3, which have two C
60groups positioned at either the
5,10- or 5,15-meso positions, show much shorter lifetime
components of 1.16 ns (86 %) and 331 ps (14 %) for 2 and
1.29 ns (81 %), and 427 ps (19 %) for 3. Similar effects were
observed for 4 and 5. From this information and the average
lifetime (t
avg) data reported in Table 1, it is clear that the
ad-dition of each C
60group leads to a decrease in the FL
life-time. These results are consistent with the F
FLdata, which
also showed a marked decrease in the F
FLvalues with each
additional C
60group. On the basis of prior photophysical
ex-periments on Por–C
60dyads in THF,
[43, 64–65]the decrease in
the t values of 1–5, compared with 8, were attributed to
photoinduced electron transfer. Electron-transfer rate
con-stants, k
ET, were calculated from the TCSPC data by using
Equation (1):
k
ET¼ ð1=t
DAÞð1=t
DÞ
ð1Þ
in which t
DAis the lifetime of 1–5 and t
Drepresents the
life-time of model porphyrin 8. The k
ETvalues shown in Table 1
were calculated by using t
1(k
ET1) and t
2(k
ET2), whereas
k
ET(avg)was calculated by using the average FL lifetime. In
the case of 5, the two shorter-lived lifetime components
were used to calculate k
ET1and k
ET2. From this data, it is
clear that the addition of each C
60group results in increases
in k
ET1and k
ET2.
Conclusion
An effective two-step sequential esterification strategy was
developed for the preparation of a series of C
60–Pors shape
amphiphiles.
The
hydroxy-functionalized Por precursors
(9–12)
were
prepared
with
high purity in a one-pot
proce-dure and all of the C
60–Por
shape amphiphiles (1–5) were
readily synthesized in good
yields in the subsequent
Steg-lich esterification reaction with
13.
Photophysical
studies
showed that the UV/Vis
ab-sorption spectra of the C
60–Por
shape amphiphiles obeyed the
simple addition of the
absorp-tion of the C
60nanoparticles
and the Por core. These results implied weak electronic
cou-pling between the C
60and Por moieties and suggested that
the relative orientation of the two moieties was close to the
edge-to-face alignment. Compared with reference molecule
8, the FL of the Por core in the C
60–Por shape amphiphiles
was significantly quenched owing to the presence of the
co-valently bonded C
60units. The FL quenching became even
more pronounced as the number of C
60units per molecule
increased from one to four. TCSPC experiments also
showed a decrease in t and an increase in k
ETof the Por
core with the addition of each C
60group. Photophysical
studies suggested the potential for the effective generation
of charge-separated species, C
60
CPor
+C, from the
photoexcit-ed C
60–Por shape amphiphiles. Further investigations are
on-going with regard to phase behavior, phase structures, and
the potential use of the C
60–Por shape amphiphiles as light
harvesters and charge-carrier generators in optoelectronic
applications.
Table 1. Summary of time-resolved FL data for 8 and the shape amphiphiles 1–5 in THF.[a]
Compounds Fluorescence lifetime kET1 kET2 kET(avg)
t1[ns] t2[ns] t3[ns] tavg[ns][b] ACHTUNGTRENNUNG[s1] ACHTUNGTRENNUNG[s1] ACHTUNGTRENNUNG[s1]
8 10.1 (100 %) 10.1 1 2.16 (71 %) 0.499 (29 %) 2.02 0.36 109 1.91 109 0.40 109 2 1.16 (63 %) 0.331 (37 %) 1.04 0.76 109 2.92 109 0.86 109 3 1.29 (59 %) 0.427 (41 %) 1.13 0.68 109 2.24 109 0.79 109 4 0.769 (61 %) 0.273 (39 %) 0.68 1.20 109 3.56 109 1.38 109 5 1.25 (4.8 %) 0.511 (43 %) 0.109 (51 %) 0.58 1.86 109 9.08 109 1.63 109
[a] An excitation wavelength of lex=560 nm and an emission wavelength of lem=651 nm were used. [b] The
average lifetimes were calculated by using the formula tavg=a1t1+a2t2+a3t3, in which anrepresents the
Experimental Section
Instrumentation
All1H and 13C NMR spectra were obtained with a Varian Gemini 300
spectrometer at 300 and 75 MHz, respectively. The1H NMR spectra were
referenced to the residual proton impurities in the CDCl3 at d =
7.27 ppm. The 13C NMR spectra were referenced to 13CDCl 3 at d =
77.00 ppm. MALDI-TOF measurements were carried out on a Bruker Ultraflex III TOF instrument (Bruker Daltonics, Inc., Billarica, MA) equipped with a Nd:YAG laser emitting at a wavelength of 355 nm. All spectra were measured in the positive reflector mode. The instrument was calibrated prior to each measurement with external standards, poly(-methyl methacrylate) and polystyrene. Data analysis was carried out by using flexAnalysis software. Absorption spectra were obtained with a Shi-madzu 1601 UV spectrometer. Steady-state FL measurements were per-formed on an ISA Jobin Yvon-SPEX Fluorolog 3-22 fluorometer with dual input and output monochromators. The samples were prepared in approximately micromolar concentrations in THF (Fischer Scientific, HPLC grade). FL spectra were collected as argon-saturated solutions by exciting at the Soret maxima in S/R mode to correct for changes in the lamp output intensity. FL spectra were also corrected for grating and de-tector response and were performed with 2.5 nm excitation and emission slit widths. Quantum yield measurements were made relative to tetraphe-nylporphyrin (FFL=0.11). Time-resolved FL experiments were
per-formed by using the TCSPC technique. The instrument used in this work utilized pulses from a Coherent cavity dumped 702 dye laser pumped by the 527 nm output of a continuous wave (CW) mode-locked Nd:YLF laser. The FL signal was detected at 54.78 with an emission polarizer and depolarizer by using a Hamamatsu R3809U-51 red-sensitive multichannel plate detector (MCP). Data collection and analysis were accomplished with an Edinburgh Instruments data collection system and the PicoQuant FluoFit decay analysis program, respectively. Time resolution on this in-strument was estimated to be about 10 ps after reconvolution. Time-re-solved decays were fit such that values of c2<1.20 were obtained. Error
limits in these measurements were estimated to be 10 %. All TCSPC experiments were run in argon-saturated solutions in THF with optical densities of between 0.10 and 0.15 at the excitation wavelength (Q-band, lex560 nm) and with detection at lex=651 nm.
Materials
Unless otherwise noted, chemicals and solvents were purchased as re-agent grade and used without further purification. CH2Cl2was purchased
from Acros as anhydrous grade. Toluene was dried over CaH2 under
argon and THF was dried over a mixture of sodium/benzophenone under argon. Both solvents were freshly distilled prior to use. 5,10,15,20-Tetra(p-hydroxyphenyl)porphyrin; 3,4,5-trisdodecyloxybenzoic acid; and the carboxylic acid derivative of methanofullerene (13) were prepared according to procedures reported in the literature.[29, 56]The synthesis of
1[46]and an analogue of 2, trans-DiC
60ZnIIPor,[44]were reported in our
previous work. The samples were kept in vacuum before characteriza-tion.
OH-Por Derivatives
3,4,5-Trisdodecyloxybenzoic acid (1.43 g, 2.12 mmol) was dissolved in CH2Cl2 (80 mL) and then slowly added to a solution of
5,10,15,20-tetra(p-hydroxyphenyl)porphyrin (0.80 g, 1.2 mmol), DIPC (318 mg, 2.50 mmol) and DPTS (633 mg, 2.12 mmol) in THF (40 mL) at 0 8C. After addition, the solution was stirred at room temperature for 1 day. The solvent was then removed in vacuo. The residue was dissolved in a mixture of CH2Cl2/hexanes (1:1) and subjected to column
chromatogra-phy (SiO2, hexanes/ethyl acetate (EA) 40:1 (v/v)). The products were
eluted out with a mixture of EA and hexanes with different ratios as shown below. After chromatography, products were reprecipitated from a THF solution with MeOH.
Compound9
Eluted with hexanes/EA = 8:1 (v/v); yield: 422 mg, 13 %; 1H NMR
(300 MHz, CDCl3): d = 8.96 (s, 4 H), 8.93 (s, 4 H), 8.30 (d, J = 8.4 Hz, 6 H), 8.09 (d, J = 8.4 Hz, 2 H), 7.65 (d, J = 8.4 Hz, 6 H), 7.62 (s, 6 H), 7.21 (d, J = 8.4 Hz, 2 H), 4.20–4.13 (m, 18 H), 1.97–1.82 (m, 18 H), 1.58 (br s, 18 H), 1.31 (br s, 144 H), 0.92–0.88 (m, 27 H), 2.75 ppm (s, 2 H); 13C NMR (75 MHz, CDCl3): d = 165.5, 155.8, 153.8, 153.3, 151.2, 143.4, 139.9, 136.0, 135.6, 134.7, 124.2, 120.5, 120.3, 119.4, 119.2, 114.0, 109.0, 73.9, 69.6, 32.2, 32.1, 30.6, 30.0, 30.0, 29.9, 29.8, 29.7, 29.6, 29.6, 26.4, 26.3, 22.9, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C173H258N4O16 [M]+: 2647.95;
found: 2647.98.
Compound10
Eluted with hexanes/EA = 3:1 (v/v); yield: 308 mg, 13 %; 1H NMR
(300 MHz, CDCl3): d = 8.91 (s, 8 H), 8.28 (d, J = 8.4 Hz, 4 H), 8.07 (d, J = 8.4 Hz, 4 H), 7.62 (d, J = 8.4 Hz, 4 H), 7.61 (s, 4 H), 7.19 (d, J = 8.4 Hz, 4 H), 4.18–4.12 (m, 12 H), 1.94–1.80 (m, 12 H), 1.59 (br s, 12 H), 1.30 (br s, 96 H), 0.90–0.87 ppm (m, 18 H); 13C NMR (75 MHz, CDCl 3): d = 165.7, 155.8, 153.3, 151.1, 143.3, 140.0, 135.9, 135.6, 134.4, 124.1, 120.5, 120.3, 119.0, 113.9, 108.9, 73.9, 69.6, 32.2, 32.1, 30.6, 30.0, 29.9, 29.9, 29.8, 29.7, 29.6, 29.6, 26.4, 26.3, 22.9, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C130H182N4O12[M] +: 1991.38; found: 1991.39. Compound11
Eluted with hexanes/EA = 3:1 (v/v); yield: 455 mg, 19 %; 1H NMR
(300 MHz, CDCl3): d = 8.96 (s, 2 H), 8.90 (s, 4 H), 8.82 (s, 2 H), 8.28 (d, J = 8.1 Hz, 4 H), 7.98 (d, J = 8.1 Hz, 4 H), 7.66 (s, 4 H), 7.61 (d, J = 8.1 Hz, 4 H), 6.98 (d, J = 8.1 Hz, 4 H), 4.22–4.18 (m, 12 H), 1.99–1.84 (m, 12 H), 1.59 (br s, 12 H), 1.33 (br s, 96 H), 0.94–0.89 ppm (m, 18 H); 13C NMR (75 MHz, CDCl3): d = 165.7, 155.8, 153.3, 151.1, 143.3, 140.0, 135.9, 135.6, 134.4, 124.1, 120.5, 120.3, 119.0, 113.9, 108.9, 74.0, 69.6, 32.2, 32.1, 30.6, 30.0, 29.9, 29.9, 29.8, 29.7, 29.6, 29.6, 26.4, 26.3, 22.9, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C130H182N4O12 [M]+: 1991.38; found:
1991.41; [M+23]+
: m/z 2014.42.
Compound12
Eluted with hexanes/EA = 2:1 (v/v); yield: 315 mg, 20 %; 1H NMR
(300 MHz, CDCl3): d = 8.90 (s, 4 H), 8.86 (s, 4 H), 8.28 (d, J = 8.4 Hz, 2 H), 8.06–8.02 (m, 6 H), 7.63–7.60 (m, 4 H), 7.18–7.11 (m, 6 H), 4.18–4.11 (m, 6 H), 1.94–1.84 (m, 6 H), 1.56 (br s, 6 H), 1.43–1.30 (m, 48 H), 0.93– 0.88 ppm (m, 9 H); 13C NMR (75 MHz, CDCl 3): d = 165.6, 155.4, 153.1, 150.9, 143.3, 139.9, 135.6, 135.4, 134.5, 123.9, 120.1, 120.0, 119.9, 118.7, 113.6, 108.9, 73.8, 69.5, 32.0, 31.9, 30.4, 29.8, 29.8, 29.7, 29.7, 29.7, 29.6, 29.5, 29.4, 29.4, 29.4, 26.2, 26.1, 22.7, 22.7, 14.1, 14.1 ppm; HRMS (MALDI-TOF): m/z calcd for C87H106N4O8 [M]
+
: 1334.80; found: 1334.43.
C60–Por Shape Amphiphiles
Compound1
Compound 13 (50 mg, 3.8 102mmol), 9 (100 mg, 3.8 102mmol), and
DPTS (11 mg, 3.8 102mmol) were dissolved in CH
2Cl2 (10 mL) and
cooled to 0 8C. DIPC (5.6 mg, 4.5 102mmol) was slowly added into the
solution by using a microsyringe. The solution was stirred at room tem-perature for 1 day. The solvent was then removed in vacuo. The residue was dissolved in hexanes/EA = 20:1 and subjected to column chromatog-raphy (SiO2, hexanes/EA = 20:1 (v/v)) to allow isolation of 1. The
ob-tained dark brown fraction was then concentrated. The product was dis-solved in CH2Cl2 and precipitated in acetone as a dark brown solid
(106 mg, 71 %).1H NMR (300 MHz, CDCl 3): d = 8.96 (s, 4 H), 8.94 (d, J = 5.1 Hz, 2 H), 8.87 (d, J = 5.1 Hz, 2 H), 8.30 (d, J = 8.4 Hz, 6 H), 8.26 (d, J = 8.7 Hz, 2 H), 7.65 (d, J = 8.4 Hz, 6 H), 7.62 (s, 6 H), 7.60 (d, J = 8.4 Hz, 2 H), 6.68 (d, J = 1.8 Hz, 2 H), 6.46 (br s, 1 H), 5.55 (s, 2 H), 5.37 (s, 2 H), 4.19–4.15 (m, 18 H), 3.94 (t, J = 6.6 Hz, 4 H), 1.96–1.71 (m, 22 H), 1.58 (br s, 18 H), 1.30–1.21 (m, 180 H), 0.91–0.83 (m, 33 H),2.78 ppm (s, 2 H); 13C NMR (75 MHz, CDCl 3): d = 165.4, 163.4, 163.2, 160.7, 153.3, 151.3, 150.1, 145.3, 145.1, 144.8, 144.8, 144.7, 143.9, 143.4, 143.1, 143.0, 142.2, 142.0, 141.9, 141.1, 141.0, 140.5, 139.8, 138.9, 136.8, 135.7, 124.2, 120.4, 119.8, 119.6, 119.1, 108.9, 107.5, 101.9, 73.9, 71.3, 69.6, 68.4, 63.1, 32.2, 32.1, 30.6, 30.0, 30.0, 29.9, 29.8, 29.7, 29.6, 29.6, 29.5, 26.4, 26.3, 22.9, 22.9, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C269H314N4O23 [M]+:
Compound2
Compound 13 (86 mg, 6.4 102mmol), 10 (58 mg, 2.9 102mmol), and
DPTS (18 mg, 6.1 102mmol) were dissolved in CH
2Cl2 (10 mL) and
cooled to 0 8C. DIPC (9.6 mg, 7.7 102mmol) was slowly added into the
solution by using a microsyringe. The solution was stirred at room tem-perature for 1 day. The solvent was then removed in vacuo. The residue was dissolved in CH2Cl2and subjected to column chromatography (SiO2,
CH2Cl2/THF = 20:1 (v/v)) to allow isolation of 2. The obtained dark
brown fraction was then concentrated. The product was dissolved in CH2Cl2 and precipitated in acetone as a black solid (91 mg, 63 %).
1H NMR (300 MHz, CDCl 3): d = 8.93 (d, J = 4.5 Hz, 4 H), 8.85 (d, J = 4.5 Hz, 4 H), 8.29–8.23 (m, 8 H), 7.66–7.58 (m, 12 H), 6.68 (d, J = 1.8 Hz, 4 H), 6.45 (br s, 2 H), 5.54 (s, 4 H), 5.36 (s, 4 H), 4.18–4.12 (12 H, m), 3.93 (t, J = 6.3 Hz, 8 H), 1.93–1.71 (m, 20 H), 1.58 (br s, 12 H), 1.30–1.21 (m, 168 H), 0.91–0.83 (m, 30 H), 2.82 ppm (s, 2 H); 13C NMR (75 MHz, CDCl3): d = 165.5, 165.4, 163.4, 163.2, 160.7, 153.3, 151.3, 150.1, 145.3, 145.1, 145.1, 145.0, 144.8, 144.7, 144.6, 143.9, 143.3, 143.1, 143.0, 143.0, 142.2, 142.0, 141.9, 141.0, 140.9, 140.5, 139.7, 138.9, 136.8, 135.7, 124.2, 120.4, 119.9, 119.7, 119.2, 108.9, 107.5, 101.9, 73.9, 71.3, 69.5, 68.4, 63.1, 32.2, 32.1, 30.6, 30.0, 30.0, 29.9, 29.8, 29.8, 29.7, 29.6, 29.6, 29.5, 26.4, 26.3, 22.9, 22.9, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C322H294N4O26
[M]+
: 4632.18; found: 4632.19.
Compound3
Compound 13 (105 mg, 7.8 102mmole), 11 (75 mg, 3.8 102mmol),
and DPTS (18 mg, 6.1 102mmol) were dissolved in CH
2Cl2 (10 mL)
and cooled to 0 8C. DIPC (12 mg, 9.4 102mmol) was slowly added into
the solution by using a microsyringe. The solution was stirred at room temperature for 1 day. The solvent was then removed in vacuo. The resi-due was dissolved in CH2Cl2and subjected to column chromatography
(SiO2, CH2Cl2/THF 20:1 (v/v)) to allow isolation of 3. The obtained dark
brown fraction was then concentrated. The product was dissolved in CH2Cl2 and precipitated in acetone as a black solid (150 mg, 83 %). 1H NMR (300 MHz, CDCl 3): d = 8.93 (m, 4 H), 8.84 (m, 4 H), 8.28 (d, J = 8.4 Hz, 4 H), 8.26 (d, J = 8.4 Hz, 4 H), 7.66–7.57 (m, 12 H), 6.67 (d, J = 1.5 Hz, 4 H), 6.45 (br s, 2 H), 5.53 (s, 4 H), 5.36 (s, 4 H), 4.18–4.12 (12 H, m), 3.93 (t, J = 6.6 Hz, 8 H), 1.93–1.71 (m, 20 H), 1.58 (br s, 12 H), 1.30– 1.21 (m, 168 H), 0.91–0.83 (m, 30 H), 2.82 ppm (s, 2 H); 13C NMR (75 MHz, CDCl3): d = 165.5, 165.4, 163.4, 163.2, 160.8, 153.3, 151.3, 150.1, 145.2, 145.2, 145.1, 145.1, 144.8, 144.7, 144.6, 144.6, 144.6, 143.8, 143.8, 143.4, 143.0, 143.0, 143.0, 142.9, 142.1, 142.0, 141.9, 141.0, 140.9, 140.5, 139.8, 139.7, 138.9, 136.8, 135.7, 124.2, 120.4, 119.9, 119.8, 119.2, 108.9, 107.5, 101.9, 73.9, 71.3, 69.6, 69.5, 68.4, 63.1, 32.2, 32.1, 30.6, 30.0, 29.9, 29.9, 29.7, 29.6, 29.6, 29.5, 26.4, 23.0, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C322H294N4O26[M]+: 4632.18; found: 4632.22.
Compound4
Compound 13 (118 mg, 8.8 102mmole), 12 (38 mg, 2.8 102mmol),
and DPTS (25 mg, 8.5 102mmol) were dissolved in CH
2Cl2 (10 mL)
and cooled to 0 8C. DIPC (13 mg, 1.0 101mmol) was slowly added into
the solution by using a microsyringe. The solution was stirred at room temperature for 1 day. The solvent was then removed in vacuo. The resi-due was dissolved in CH2Cl2and subjected to column chromatography
(SiO2, CH2Cl2/THF = 10:1 (v/v)) to allow isolation of 4. The obtained
dark brown fraction was then concentrated. The product was dissolved in CH2Cl2 and precipitated in acetone as a black solid (114 mg, 73 %).
1H NMR (300 MHz, CDCl 3): d = 8.91 (d, J = 4.8, 2 H), 8.84 (d, J = 4.8, 2 H), 8.81 (s, 4 H), 8.26 (d, J = 8.4, 2 H), 8.23–8.19 (m, 6 H), 7.64 (d, J = 8.4 Hz, 2 H), 7.61ACHTUNGTRENNUNG(s, 2H), 7.58 (d, J= 8.4 Hz, 6 H), 6.66 (d, J =2.1 Hz, 6 H), 6.45 (t, J = 2.1 Hz, 3 H), 5.53 (s, 6 H), 5.34 (s, 6 H), 4.18–4.12 (6 H, m), 3.93 (t, J = 6.6 Hz, 12 H), 1.92–1.75 (m, 18 H), 1.55 (br s, 6 H), 1.42– 1.22 (m, 156 H), 0.91–0.83 (m, 27 H), 2.82 ppm (s, 2 H); 13C NMR (75 MHz, CDCl3): d = 165.5, 163.4, 163.2, 160.8, 153.3, 151.3, 150.1, 145.2, 145.2, 145.1, 145.0, 144.8, 144.7, 144.6, 144.5, 143.8, 143.8, 143.7, 143.0, 143.0, 142.9, 142.9, 142.1, 142.0, 141.9, 141.0, 141.0, 140.5, 139.7, 138.9, 136.8, 135.7, 124.2, 120.4, 119.9, 119.3, 109.0, 107.5, 101.9, 73.9, 71.3, 69.6, 69.4, 68.4, 63.1, 32.2, 32.1, 30.6, 30.0, 30.0, 29.9, 29.8, 29.7, 29.6, 29.6, 29.5,
26.4, 22.9, 22.9, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C375H275N4O29[M+H]+: 5297.02; found: 5297.04.
Compound5
Compound 13 (120 mg, 9.0 102mmol),
5,10,15,20-tetra(p-hydroxyphe-nyl)porphyrin (14 mg, 2.1 102mmol), and DPTS (24 mg, 8.4
102mmol) were dissolved in THF/CH
2Cl2(1:2, 12 mL v/v) and cooled to
0 8C. DIPC (14 mg, 1.1 101mmol) was slowly added into the solution
by using a microsyringe. The solution was stirred at room temperature for 2 days. The solvent was then removed in vacuo. The residue was dis-solved in CH2Cl2 and subjected to column chromatography (SiO2,
CH2Cl2/THF = 10:1 (v/v)) to allow isolation of 5. The obtained dark
brown fraction was then concentrated. The product was dissolved in CH2Cl2 and precipitated in acetone as a black solid (71 mg, 53 %). 1H NMR (300 MHz, CDCl 3): d = 8.79 (s, 8 H), 8.18 (d, J = 8.1, 8 H), 7.56 (d, J = 8.1 Hz, 8 H), 6.65 (d, J = 1.5 Hz, 8 H), 6.44 (br s, 4 H), 5.52 (s, 8 H), 5.33 (s, 8 H), 3.92 (t, J = 6.3 Hz, 16 H), 1.78–1.73 (m, 16 H), 1.43 (br s, 16 H), 1.23 (br s, 128 H), 0.858 (t, J = 6.6 Hz, 24 H),2.82 ppm (s, 2 H); 13C NMR (75 MHz, CDCl 3): d = 165.5, 163.4, 163.2, 160.7, 150.1, 145.1, 145.0, 144.9, 144.6, 144.5, 144.4, 144.3, 143.7, 143.6, 142.9, 142.9, 142.8, 142.8, 142.7, 142.0, 141.8, 141.7, 140.9, 140.8, 140.4, 139.6, 138.9, 136.8, 135.7, 119.9, 119.4, 107.5, 101.8, 71.2, 69.4, 68.4, 63.1, 51.3, 32.1, 29.9, 29.9, 29.7, 29.6, 29.5, 26.4, 22.9, 14.4 ppm; HRMS (MALDI-TOF): m/z calcd for C428H255N4O32[M+H]+: 5960.84; found: 5960.93.
Acknowledgements
This work was supported by the National Science Foundation (DMR-0906898, S.Z.D.C. and CHE-0216371, D.A.M.), the Collaborative Center for Polymer Photonics, AFOSR, the Joint-Hope Foundation, and the Na-tional Science Council of Taiwan (NSC100-2221-E-009-152-MY3). We ap-preciate Dr. Xiaopeng Li and Prof. Chrys Wesdemiotis for assistance with the MALDI-TOF mass spectra measurements.
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Received: November 15, 2012 Published online: February 20, 2013
![Table 1. Summary of time-resolved FL data for 8 and the shape amphiphiles 1–5 in THF. [a]](https://thumb-ap.123doks.com/thumbv2/9libinfo/7627522.133936/6.892.70.616.545.668/table-summary-time-resolved-data-shape-amphiphiles-thf.webp)
